3004 J . Org. Chem., Vol. 67, No. 9, 2002
Belelie and Chong
29.3, 26.1, 21.7, 19.9 (2C), 18.6 (2C); MS (EI) m/z (%) 231 (M+
- i-Pr, 0.6), 91 (100). Anal. Calcd for C19H30O: C, 83.15; H,
11.02. Found: C, 83.40; H, 10.81.
127.5 (2C); 127.2; 125.9*, 125.8; 124.8; 80.0, 79.9*; 71.0; 50.9,
50.5*; 26.0; 18.2; 17.9*, 17.5; MS (EI) m/z (%) 173 (M+ - OBn,
4), 91 (100). Anal. Calcd for C20H24O: C, 85.67; H, 8.63.
Found: C, 85.50; H, 8.48.
5-Ben zyloxy-4-ter t-bu tyl-2-m eth yl-2-h exen e (9a ). Gen-
eral procedure A was followed using acetate 4a (200 mg, 0.76
mmol), t-BuMgCl (1.5 mL, 1.03 M, 1.6 mmol), and CuCN (7
mg, 0.08 mmol). The crude oil (anti:syn ) 83:17 by GC/MS
analysis) was purified via column chromatography (6:1 hexane:
CH2Cl2) to give 144 mg of a n ti-9a and 32 mg of syn -9a (total
5-Ben zyloxy-2-m eth yl-4-p h en yl-2-n on en e (10b). Gen-
eral procedure A was followed using acetate 4b (201 mg, 0.66
mmol), PhMgBr (0.47 mL, 2.82 M, 1.3 mmol), and CuCN (31
1
mg, 0.34 mmol). The crude oil (anti:syn ) 88:12 by H NMR
analysis) was purified via column chromatography (4:1 hexane:
CH2Cl2) to give 145 mg (68%) of a clear, colorless oil: IR (neat)
1671, 1093, 699 cm-1; 1H NMR (300 MHz, CDCl3) δ 7.33-7.18
(10H, m), 5.63 (0.88H, d, J ) 9.4 Hz), 5.47 (0.12H, J ) 9.5
Hz), 4.44 (1H, A of AB, d, J obs ) 11.3 Hz), 4.38 (1H, B of AB,
d, J obs ) 11.3 Hz), 3.71 (1H, dd, J ) 9.5, 5.1 Hz), 3.60-3.54
(1H, m), 1.76 (2.64H, s), 1.72 (0.36H, s), 1.64 (0.36H, s), 1.61
(2.64H, s), 1.47-1.35 (2H, m), 1.35-1.20 (4H, m), 0.88-0.82
(3H, m); 13C NMR (75 MHz, CDCl3) δ 143.7*, 143.5; 138.9*,
138.6; 133.2*, 132.7; 128.5, 128.3* (2C); 128.2 (2C); 128.1 (2C);
128.0, 127.9* (2C); 127.7, 127.3*; 125.9; 124.8, 124.4*; 83.6;
72.5, 72.4*; 49.0, 48.3*; 32.3*, 31.8; 28.0*, 27.7; 26.1, 26.0*;
22.8; 18.2; 14.1; MS (EI) m/z (%) 265 (M+ - n-Bu, 0.1), 91 (100).
Anal. Calcd for C23H30O: C, 85.66; H, 9.38. Found: C, 85.72;
H, 9.48.
176 mg, 89%) as clear, colorless oils: IR (neat) 1672, 696 cm-1
;
1H NMR (300 MHz, CDCl3) a n ti-9a , δ 7.34-7.26 (5H, m), 5.41
(1H, d, J ) 11.0 Hz), 4.60 (1H, A of AB, d, J obs ) 11.7 Hz),
4.38 (1H, B of AB, J obs ) 11.7 Hz), 3.90 (1H, qd, J ) 6.2, 1.6
Hz), 1.92 (1H, dd, J ) 11.0, 1.6 Hz), 1.78 (3H, s), 1.59 (3H, s),
1.08 (3H, d, J ) 6.2 Hz), 0.91 (9H, s); syn -9a , δ 7.36-7.24 (5H,
m), 5.06 (1H, d, J ) 11.0 Hz), 4.51 (2H, m), 3.62 (1H, qd, J )
6.1, 5.0 Hz), 2.40 (1H, dd, J ) 11.0, 5.0 Hz), 1.75 (3H, s), 1.65
(3H, s), 1.13 (3H, d, J ) 6.1 Hz), 0.90 (3H, s); 13C NMR (75
MHz, CDCl3) a n ti-9a , δ 139.3, 133.0, 128.1 (2C), 127.4, 127.1
(2C), 122.3, 75.0, 70.2, 53.5, 34.2, 28.8 (3C), 26.3, 18.6, 18.3;
syn -9a , δ 139.1, 132.8, 128.2 (2C), 127.7 (2C), 127.3, 123.2,
76.0, 70.1, 51.7, 33.4, 28.7 (3C), 26.2, 18.5, 18.1; MS (EI) m/z
(%) both diastereomers: 91 (100). Anal. Calcd for C18H28O: C,
83.02; H, 10.84. Found: C, 83.29; H, 10.61.
5-Ben zyloxy-2,6-dim eth yl-4-ph en yl-2-h epten e (10c). Gen-
eral procedure A was followed using acetate 4c (201 mg, 0.69
mmol), PhMgBr (0.49 mL, 2.82 M, 1.4 mmol), and CuCN (32
mg, 0.36 mmol). The crude oil (only one isomer by GC/MS
analysis) was purified via column chromatography (6:1 hexane:
CH2Cl2) to give 160 mg (75%) of a clear, colorless oil: IR (neat)
1671, 699 cm-1; 1H NMR (300 MHz, CDCl3) δ 7.32-7.16 (10H,
m), 5.67 (1H, d, J ) 9.6 Hz), 4.32 (1H, A of AB, d, J obs ) 10.7
Hz), 4.13 (1H, B of AB, d, J obs ) 10.7 Hz), 3.78 (1H, dd, J )
9.6, 5.6 Hz), 3.31 (1H, dd, J ) 5.6, 5.6 Hz), 1.73 (3H, s), 1.72-
1.66 (1H, m), 1.59 (3H, s), 0.97 (3H, d, J ) 7.5 Hz), 0.92 (3H,
d, J ) 7.3 Hz); 13C NMR (75 MHz, CDCl3) δ 144.0, 139.0, 132.9,
128.4 (2C), 128.3 (2C), 128.1 (2C), 127.9 (2C), 127.3, 125.9,
124.2, 89.6, 75.2, 47.1, 31.4, 26.0, 20.1, 18.2, 18.0; MS (EI) m/z
(%) 265 (M+ - i-Pr, 0.3), 91 (100). Anal. Calcd for C22H28O: C,
85.66; H, 9.15. Found: C, 85.80; H, 9.12.
5-Ben zyloxy-4-ter t-bu tyl-2-m eth yl-2-n on en e (9b). Gen-
eral procedure A was followed using acetate 4b (202 mg, 0.66
mmol), t-BuMgCl (1.3 mL, 1.03 M, 1.3 mmol), and CuCN (6
mg, 0.07 mmol). The crude oil (anti:syn ) 87:13 by GC/MS
analysis) was purified via column chromatography (10:1
hexane:CH2Cl2) to give 180 mg (89%) of a clear, colorless oil:
IR (neat) 1671, 696 cm-1; 1H NMR (300 MHz, CDCl3) δ 7.34-
7.26 (5H, m), 5.41 (0.87H, d, J ) 11.0 Hz), 5.10 (0.13H, d, J )
9.2 Hz), 4.58 (0.87H, A of AB, d, J obs ) 11.6 Hz), 4.55 (0.13H,
A of AB, d, J obs ) 10.2 Hz), 4.43 (0.87H, B of AB, d, J obs ) 11.6
Hz), 4.39 (0.13H, B of AB, d, J obs ) 10.2 Hz), 3.62-3.58 (0.87H,
m), 3.51-3.45 (0.13H, m), 2.48-2.44 (0.13H, m), 2.06 (0.87H,
d, J ) 11.0 Hz), 1.77 (2.61H, s), 1.74 (0.39H, s), 1.64 (0.39H,
s), 1.59 (2.61H, s), 1.42-1.15 (6H, m) 0.91 (9H, s), 0.91 (3H,
m); 13C NMR (75 MHz, CDCl3) δ 139.3*, 138.9; 132.9*, 132.7;
128.2, 128.1* (2C); 127.4*, 127.3 (2C); 127.1; 123.0, 122.5*;
80.1, 79.9*; 70.6; 50.3*, 49.5; 34.1*, 33.2; 32.1*, 32.0; 28.9*,
28.8 (3C); 28.7*, 28.1; 26.3; 23.0*, 22.8; 18.5*, 18.4; 14.2, 14.1*;
MS (EI) m/z (%) 245 (M+ - t-Bu, 0.1), 91 (100). Anal. Calcd
for C21H34O: C, 83.38; H, 11.33. Found: C, 83.52; H, 11.42.
5-Ben zyloxy-4-ter t-bu tyl-2,6-d im eth yl-2-h ep ten e (9c).
General procedure A was followed using acetate 4c (499 mg,
1.7 mmol), t-BuMgCl (3.3 mL, 1.03 M, 3.4 mmol), and CuCN
(17 mg, 0.19 mmol) to give 464 mg (94%) of a clear, colorless
oil. The resulting product was sufficiently clean and did not
5-Ben zyloxy-2,4,6-tr im eth yl-2-h ep ten e (11c). General
procedure A was followed using acetate 4c (152 mg, 0.52
mmol), MeMgBr (0.35 mL, 2.94 M, 1.0 mmol), and CuCN (26
mg, 0.29 mmol). The crude oil (anti:syn ) 98:2 by GC/MS
analysis) was purified via column chromatography (6:1 hexane:
CH2Cl2) to give 99 mg (77%) of a clear, colorless oil: IR (neat)
1672, 697 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.36-7.24 (5H,
m), 5.21 (1H, d, J ) 9.6 Hz), 4.61 (1H, A of AB quartet, d, J obs
) 11.2 Hz), 4.56 (1H, B of AB quartet, d, J obs ) 11.2 Hz), 2.93
(1H, dd, J ) 6.5, 4.6 Hz), 2.69-2.63 (1H, m), 1.80 (1H, qqd, J
) 6.9, 6.7, 6.5 Hz), 1.69 (3H, s), 1.61 (3H, s), 0.99 (3H, d, J )
1
require purification: IR (neat) 1671, 696 cm-1; H NMR (300
MHz, CDCl3) δ 7.38-7.22 (5H, m), 5.49 (1H, d, J ) 10.8 Hz),
4.61 (1H, A of AB, d, J obs ) 11.5 Hz), 4.57 (1H, B of AB, d, J obs
) 11.5 Hz), 3.39 (1H, d, J ) 6.9 Hz), 2.17 (1H, d, J ) 10.8 Hz),
1.87 (1H, dqq, J ) 6.9, 6.9, 6.8 Hz), 1.74 (3H, s), 1.59 (3H, s),
0.98 (3H, d, J ) 6.9 Hz), 0.91 (9H, s), 0.87 (3H, d, J ) 6.8 Hz);
13C NMR (75 MHz, CDCl3) δ 139.5, 131.7, 128.1 (2C), 127.0
(3C), 123.6, 84.3, 72.3, 48.7, 34.4, 32.2, 28.7 (3C), 26.3, 19.4,
19.0, 18.8; MS (EI) m/z (%) 245 (M+ - i-Pr, 0.3), 91 (100). Anal.
Calcd for C20H32O: C, 83.27; H, 11.18. Found: C, 83.09; H,
11.15.
6.9 Hz), 0.98 (3H, d, J ) 6.7 Hz), 0.90 (3H, d, J ) 6.8 Hz); 13
C
NMR (75 MHz, CDCl3) δ 139.4, 130.5, 128.2 (2C), 127.5 (2C),
127.3, 127.2, 89.6, 75.1, 35.6, 31.3, 25.9, 20.0, 19.0, 18.3, 17.9;
MS (EI) m/z (%) 246 (M+, 0.03), 91 (100). Anal. Calcd for
C
17H26O: C, 82.89; H, 10.64. Found: C, 82.55; H, 10.60.
5-Ben zyloxy-4-eth yl-2,6-d im eth yl-2-h ep ten e (12c). Gen-
eral procedure A was followed using acetate 4c (151 mg, 0.52
mmol), EtMgBr (0.55 mL, 1.89 M, 1.0 mmol), and CuCN (24
mg, 0.26 mmol). The crude oil (anti:syn ) 99:1 by GC/MS
analysis) was purified via column chromatography (6:1 hexane:
CH2Cl2) to give 114 mg (84%) of a clear, colorless oil: IR (neat)
1672, 1097, 697 cm-1; 1H NMR (500 MHz, CDCl3) δ 7.37-7.24
(5H, m), 5.16 (1H, d, J ) 10.3 Hz), 4.60-4.55 (2H, m), 3.02
(1H, dd, J ) 7.4, 3.6 Hz), 2.42-2.37 (1H, m), 1.79 (1H, dqq, J
) 7.4, 6.8, 6.7 Hz), 1.72 (3H, s), 1.61 (3H, s), 1.55-1.48 (1H, A
of AB, m), 1.41-1.35 (1H, B of AB, m), 0.98 (3H, d, J ) 6.7
Hz), 0.88 (3H, d, J ) 6.8 Hz), 0.84 (3H, t, J ) 7.4 Hz); 13C
NMR (75 MHz, CDCl3) δ 139.4, 131.9, 128.2 (2C), 127.5 (2C),
127.2, 125.5, 88.8, 75.0, 43.1, 31.6, 26.3, 26.0, 19.9, 19.0, 18.4,
12.2; MS (EI) m/z (%) 217 (M+ - i-Pr, 0.7), 91 (100). Anal. Calcd
for C18H28O: C, 83.02; H, 10.84. Found: C, 83.21; H, 10.76.
4-Bu t yl-5-ter t-b u t yld im et h ylsilyloxy-2-m et h yl-2-n on -
en e (13b). General procedure A was followed using acetate
5b (149 mg, 0.45 mmol), n-BuMgBr (0.51 mL, 2.77 M, 1.4
mmol), and CuCN (6 mg, 0.07 mmol). The crude oil (anti:syn
5-Ben zyloxy-2-m eth yl-4-p h en yl-2-h exen e (10a ). General
procedure A was followed using acetate 4a (202 mg, 0.77
mmol), PhMgBr (0.54 mL, 2.82 M, 1.5 mmol), and CuCN (37
1
mg, 0.41 mmol). The crude oil (anti:syn ) 79:21 by H NMR
analysis) was purified via column chromatography (3:2 hexane:
CH2Cl2) to give 139 mg (64%) of a clear, colorless oil: IR (neat)
1672, 699 cm-1; 1H NMR (300 MHz, CDCl3) δ 7.31-7.18 (10H,
m), 5.58 (0.79H, d, J ) 9.4 Hz), 5.42 (0.21H, d, J ) 9.3 Hz),
4.57 (0.79H, A of AB, d, J obs ) 12.0 Hz), 4.48 (0.21H, A of AB,
d, J obs ) 11.6 Hz), 4.43 (0.79H, B of AB, d, J obs ) 12.0 Hz),
4.27 (0.21H, B of AB, d, J obs ) 11.6 Hz), 3.75-3.65 (1H, m),
3.62-3.55 (1H, m), 1.75 (2.37H, s), 1.72 (0.63H, s), 1.65 (0.63H,
s), 1.61 (2.37H, s), 1.20 (0.63H, d, J ) 5.9 Hz), 1.09 (2.37H, d,
J ) 6.2 Hz); 13C NMR (75 MHz, CDCl3) δ 143.4; 138.9*, 138.6;
133.1*, 132.9; 128.8*, 128.7 (2C); 128.2 (2C); 128.1*, 128.0 (2C);